WO2017222084A1 - Production method for product derived from plant-based biomass having two-stage process - Google Patents

Abstract

A production method for a product derived from a plant-based biomass that includes: a processing step (1) for separating a hemicellulose from a plant-based biomass; and a processing step (2) for mixing the solid component obtained from processing step (1) with a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water, and heat-treating the mixture.

Description

Method for producing plant biomass-derived product by a two-stage process

The present invention relates to a method for producing a plant biomass-derived product having a two-stage process.

With the recent increase in environmental awareness, biomass-derived raw materials have been desired. However, raw materials derived from biomass are particularly prominent in the production of bioethanol, for example, but there are many cases where raw materials that compete with food such as starch and sugar are often used, which leads to an increase in food prices and a decrease in food production. Was pointed out. Therefore, a technology for producing biofuels and biochemicals from cellulosic biomass that does not compete with food is currently attracting attention.
Cellulosic biomass includes, for example, palm palm trunks and bunches, palm palm fruit fibers and seeds, bagasse (sugar cane (including high biomass and sugar cane)), cane top (sugar cane top and leaf), rice straw, Straw, rice husk, corn cobs, foliage, corn residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed coat and shell, cashew shell, wood chip, switchgrass, napiergrass, Eliansus Energy crops and energy canes. These cellulosic biomasses contain lignin in addition to cellulose and hemicellulose that can be converted into sugar.

In order to obtain sugar from cellulosic biomass, a pretreatment step is usually required before the enzymatic saccharification treatment. By the pretreatment, each component of the biomass or a bond between the components is loosened, and the enzyme can easily access the cellulose. However, since the enzyme adsorbs to lignin present in the system and inhibits saccharification, it was necessary to use a large amount of expensive enzyme in order to obtain sufficient saccharification, so that lignin was solubilized. It was desired.
In addition, hemicellulose is excessively decomposed when exposed to high temperature, and is easily converted into a saccharification / fermentation inhibitor such as furfural, and it is necessary to suppress the excessive decomposition.
Lignin is usually produced as a residue when biomass is converted to ethanol, but has been limited to use as a fuel because it contains many impurities such as enzymes and yeast. However, since it has a polyphenol-like structure, it can be expected to be converted into chemicals and bioplastics, and therefore it is desired to extract lignin.

Patent Document 1 discloses a lignin derivative that undergoes a treatment step in which biomass is stirred in the presence of a solvent under high temperature and high pressure.
In Patent Document 2, biomass is recovered in the presence of a mixed solvent containing water and an aprotic polar solvent, and these are decomposed under high temperature and high pressure to recover a cellulose derivative, a lignin derivative, and a hemicellulose derivative. It is disclosed.
Patent Document 3 includes a 1,1-diphenylpropane unit grafted with a phenol derivative at the α-position of a phenylpropane unit of lignin, and has an ester site in which one or two or more hydroxyl groups are acylated. Based polymers are disclosed.

Japanese Patent No. 5256679 Japanese Patent Laid-Open No. 2014-62051 JP 2011-256381 A

However, many of the lignins obtained in Patent Document 1 have a molecular weight that is too low, and the heat resistance is poor when lignin is used as a resin, and in order to improve workability, secondary induction is performed separately in a reaction kettle. The lignin as such was difficult to use. Moreover, there is no detailed description regarding hemicellulose and saccharides of cellulose.
In the method described in Patent Document 2, the decomposition treatment temperature is high, and hemicellulose is excessively decomposed, so that it is difficult to recover the sugar. There is no detailed description of the properties of cellulose derivatives. It has also been disclosed that the material is homogenized by acylation modification with a hydroxyl group of lignin, and it has been necessary to perform secondary derivatization in a separate reaction vessel. In addition, although the heat resistance is increased, the phenolic hydroxyl group is crushed, so that the reaction point is also lost, which is attractive as a material.
Patent Document 3 discloses that the material is homogenized by acylating and modifying the hydroxyl group of lignin. In this method, secondary derivatization is required, and although the heat resistance is increased, the phenolic hydroxyl group is crushed. Therefore, the reactive sites are also lost, which is attractive as a material.

The present invention is to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass.

As a result of intensive studies, the present inventors have found that the above problems can be solved by going through the following specific two-stage process.
That is, the present invention provides the following [1] to [17].
[1] A processing step (1) for separating hemicellulose from plant biomass, a solid content obtained from the processing step (1), and a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water The manufacturing method of the plant biomass origin product containing the process process (2) which mixes and heat-processes.
[2] The plant-derived biomass-derived product according to the above [1], wherein after the treatment step (2), solid-liquid separation is performed to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid. Production method.
[3] The method for producing a plant biomass-derived product according to [2] above, wherein solid lignin is obtained by removing a solvent from the lignin-containing solution.
[4] The method for producing a plant biomass-derived product according to any one of the above [1] to [3], wherein the plant biomass is a herbaceous biomass.
[5] The method for producing a plant-derived biomass-derived product according to any one of [1] to [4], wherein in the treatment step (1), hydrothermal treatment is performed as a treatment for separating hemicellulose.
[6] The plant according to [5], wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam explosion, and hydrothermal treatment using an acidic aqueous solution. Of producing a biomass-derived product.
[7] The method for producing a plant biomass-derived product according to the above [6], wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from inorganic acids and organic acids.
[8] The pH of the system from after the separation of hemicellulose in the treatment step (1) to before mixing the solid content obtained from the treatment step (1) in the treatment step (2) and the solvent, or the treatment step (2 The pH of the system at the time of mixing the solid content obtained from the treatment step (1) and the solvent in step 1) is adjusted using a basic substance, according to any one of [1] to [7] above A method for producing a plant biomass-derived product.
[9] The plant biomass-derived product according to [8] above, wherein in the treatment step (2), the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed is adjusted. Production method.
[10] The method for producing a plant-derived biomass-derived product according to [8] or [9] above, wherein the pH of the system after adjusting the pH using the basic substance is 3 or more and 12 or less.
[11] The above [1] to [1], wherein the organic solvent used in the treatment step (2) is at least one selected from ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and acetone. 10] The manufacturing method of the plant biomass origin product as described in any one of [10].
[12] The method for producing a plant-derived biomass-derived product according to any one of [1] to [11], wherein the treatment step (2) is performed under the following conditions A to C.
Condition A: The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is 1% by mass or more and 50% by mass or less.
Condition B: treatment temperature is 100 ° C. or more and 300 ° C. or less, and condition C: treatment time is 0.1 hour or more and 10 hours or less.
[13] A method for producing glucose in which glucose is obtained by subjecting a cellulose-containing solid obtained by the production method according to any one of [2] to [12] to an enzymatic saccharification treatment.
[14] A resin composition comprising the lignin obtained by the method according to any one of [2] to [12] above.
[15] A lignin satisfying the following (11) to (13).
(11): The purity of lignin is 90% or more,
(12): Number average molecular weight is 650 or more, and (13): 5% thermogravimetric decrease starting temperature is 210 ° C. or more.
[16] A resin composition comprising the lignin according to [15].
[17] A molded product comprising the resin composition according to [14] or [16].

According to the present invention, it is possible to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the excessive decomposition of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharide and the cellulose-containing solid.

The method for producing a plant biomass-derived product of the present invention includes a treatment step (1) for separating hemicellulose from a plant biomass, a solid content obtained from the treatment step (1), and an organic solvent alone or an organic solvent. It has the process containing the process process (2) which mixes the solvent selected from the mixed solvent with water, and heat-processes. Hereinafter, embodiments of the present invention will be described in detail.

<Processing step (1)>
In this step, hemicellulose is separated from plant biomass. Details will be described below.

[Plant biomass]
Examples of plant biomass include woody biomass and herbaceous biomass. Examples of woody biomass include conifers such as cedar, cypress, hiba, cherry, eucalyptus, beech and bamboo, and broad-leaved trees.
Herbaceous biomass includes palm palm trunks and empty bunches, palm palm fruit fibers and seeds, bagasse (sugar cane and high biomass sugar cane squeezed rice cake), cane top (sugar cane top and leaf), energy cane, rice straw, straw, Corn cob, foliage, residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed shell and shell, cashew shell, switchgrass, Elianthus, high biomass yield crop, energy crop, Energy cane etc. are mentioned.
Among these, from the viewpoint of availability and compatibility with the production method applied in the present invention, it is preferably a herbaceous biomass, palm palm empty bunch, straw, corn stover and residue, bagasse, cane top, Energy cane and residues after extraction of these useful components are more preferred, bagasse, cane top and energy cane are more preferred, and bagasse, cane top and energy cane are even more preferred.
The plant biomass can be pulverized. Moreover, any shape of a block, a chip, or powder may be used. Furthermore, it may be either dry or hydrated.

[Processing conditions]
As the treatment step (1) for separating hemicellulose, a known plant biomass treatment method can be used, but hydrothermal treatment is preferably performed here. Examples of the hydrothermal treatment include at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam explosion, and hydrothermal treatment using an acidic aqueous solution.
When hydrothermal treatment using an acidic aqueous solution is performed, it is preferable to use an acidic aqueous solution containing at least one selected from inorganic acids and organic acids. Among them, at least one acid aqueous solution selected from the group consisting of inorganic acids selected from dilute sulfuric acid, phosphoric acid, dilute hydrochloric acid and dilute nitric acid, and organic acids selected from formic acid, acetic acid, oxalic acid and malic acid, It can be used as an acidic aqueous solution.

In the treatment step (1), the charged concentration of the plant-based biomass as the raw material with respect to the aqueous solvent is usually 1% by mass to 95% by mass, preferably 3% by mass to 80% by mass, more preferably 5% by mass. % To 50% by mass, most preferably 5% to 20% by mass.
If the feed concentration of the raw material plant biomass is 1% by mass or more, the amount of energy used for heating the aqueous solvent can be suppressed, and the energy efficiency of the treatment step (1) can be kept good. When the feed concentration of the raw material plant-based biomass is 95% by mass or less, the separation efficiency can be kept good.

The treatment temperature in the treatment step (1) is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 190 ° C. or lower, and further preferably 150 ° C. or higher and 180 ° C. or lower. If it is 50 degreeC or more, hemicellulose can be solubilized. If it is 200 degrees C or less, the excessive decomposition of hemicellulose can be suppressed.
The treatment time in the treatment step (1) is preferably from 1 minute to 5 hours, more preferably from 3 minutes to 3 hours, further preferably from 5 minutes to 2 hours, particularly preferably from 10 minutes to 1 hour. Below time. If the treatment time is 1 minute or longer, hemicellulose can be solubilized. If the treatment time is 5 hours or less, the excessive decomposition of hemicellulose can be suppressed.
The pressure of the reaction system in the treatment step (1) is desirably 0.1 MPa to 30 MPa. More preferable conditions are appropriately set because they are affected by temperature. Further, the treatment process can be performed in an ambient atmosphere.
Although there is no restriction | limiting in particular in the processing method in a process process (1), A stationary or stirring process can be mentioned. For example, a general batch reactor, semi-batch reactor, pressure vessel, or the like can be used. Moreover, the system which processes, extruding the slurry which consists of a plant biomass origin solid substance, water, or acidic aqueous solution with a screw or a pump etc. is applicable.

Hemicellulose is separated by solid-liquid separation of the reaction product after hydrothermal treatment. In addition, as solid after solid-liquid separation, the solid content containing a cellulose and lignin is obtained.
In addition, in the process process (1), the process of washing the obtained solid content with water may be included. For example, 100 parts by mass or more and 10000 parts by mass or less of water are added to 100 parts by mass of the obtained solids and stirred, and then the solids and the liquid phase are separated by filtration. The amount of water used for the water washing is more preferably 1000 parts by mass or more and 5000 parts by mass or less, and still more preferably 1000 parts by mass or more and 2000 parts by mass or less. If the amount of water used for water washing is 100 parts by mass or more, a sufficient cleaning effect can be obtained, and if it is 10000 parts by mass or less, it can be carried out without any problems in terms of equipment. By providing this washing step, water-soluble components such as hemicellulose-derived saccharides can be removed from the solid content.
A method for performing solid-liquid separation is not particularly limited, and examples thereof include filtration, filter press, centrifugal separation, and dehydrator.

<Processing step (2)>
This treatment step is a step in which the solid content obtained from the treatment step (1) and a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water are mixed and subjected to heat treatment. In this step, lignin and cellulose are separated.
As the solvent, an organic solvent alone or a solvent selected from a mixed solvent of an organic solvent and water is used.

[Organic solvent]
The organic solvent is not particularly limited, and may be a saturated or unsaturated linear alcohol or branched alcohol. In addition, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol, and polyethylene glycol may be used. Moreover, the organic solvent may be used alone or in combination.
Among them, at least one selected from methanol, ethanol, propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, hexanol, heptanol, octanol, acetone and tetrahydrofuran And more preferably at least one selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone, and 1-butanol, 2-methyl-1- More preferably, it is at least one selected from propanol, 2-butanol, ethanol and acetone, more preferably 1-butanol, 2-methyl-1-propanol, 2-butanol, and 1-butanol. It is particularly preferred.

[Mixed solvent]
When using the mixed solvent of the said organic solvent and water, as an organic solvent, what was mentioned above can be used and a preferable thing is also the same. Examples of water that can be used include tap water, industrial water, ion exchange water, and distilled water.
The concentration of the organic solvent in the mixed solvent is preferably 10% by weight to 80% by weight, more preferably 12% by weight to 75% by weight, and further preferably 15% by weight to 70% by weight. If the concentration of the organic solvent in the mixed solvent is within the above-described range, lignin can be sufficiently separated in the treatment step (2).

Here, the pH of the system from after the separation of hemicellulose in the processing step (1) until before mixing the solid content and the solvent obtained from the processing step (1) in the processing step (2), or in the processing step (2) It is preferable to perform the heat treatment in the treatment step (2) after adjusting the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed with a basic substance. In particular, when hydrothermal treatment is performed using an acidic aqueous solution in the treatment step (1), it is preferable to adjust the pH before the heat treatment in the treatment step (2).
Since the processing conditions of the processing step (2) are stricter than those of the processing step (1), if the pH in the system is inclined to be acidic, the cellulose obtained in the processing step (2) may cause undesirable overdegradation. . In order to suppress this excessive decomposition, it is preferable to adjust the pH before mixing the solid content obtained from the treatment step (1) and the solvent in the treatment step (2).
Examples of the basic substance include inorganic bases such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and organic bases such as ammonia. The pH before heating in the treatment step (2) is preferably 3 or more and 12 or less, more preferably 3 or more and 10 or less, still more preferably 4 or more and 8 or less, particularly preferably 4 or more and 7 or less, and most preferably 4 Adjust to 6 or less. By making pH into the said range, the excessive decomposition of a cellulose can be suppressed and a high sugar yield is obtained.

[Processing conditions]
The treatment conditions in the treatment step (2) are preferably performed under conditions that satisfy all of the following conditions A to C.
Condition A
The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is preferably 1% by mass or more and 50% by mass or less. In addition, when using a some organic solvent as a solvent, the preparation density | concentration of the said solid content is with respect to the total amount of a solvent. If the solid concentration obtained from the treatment step (1) is 1% by mass or more, the energy efficiency of the lignin removal process even if the amount of energy used for heating the solvent or removing the organic solvent is taken into account. Can be kept good. If the preparation concentration of the solid content is 50% by mass or less, the amount of the solvent is sufficient, so that the lignin separation efficiency can be kept good.
The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.

Condition B
The treatment temperature in the treatment step (2) is preferably 100 ° C. or higher and 300 ° C. or lower. If the treatment temperature is 100 ° C. or higher, the lignin can be sufficiently separated, and if it is 300 ° C. or lower, decomposition of cellulose and generation of impurities such as coke due to repolymerization of lignin can be suppressed. .
The treatment temperature is more preferably 150 ° C. or higher and 250 ° C. or lower, and further preferably 170 ° C. or higher and 230 ° C. or lower.

Condition C
The treatment time in the treatment step (2) is preferably 0.1 hour or more and 10 hours or less. If the treatment time is 0.1 hour or more, the separation of lignin can be sufficiently advanced, and if it is 10 hours or less, the decomposition of cellulose and the generation of impurities such as coke due to repolymerization of lignin are suppressed. Can do.
The treatment time is more preferably 0.2 hours or more and 8 hours or less, further preferably 1 hour or more and 6 hours or less, and particularly preferably 1 hour or more and 3 hours or less.

As another processing condition in the processing step (2), it is desired that the pressure of the reaction system is 0.5 MPa to 30 MPa. However, the preferable range of the pressure in the reaction system is appropriately set because it is influenced by the amount of water and organic solvent and the temperature. The processing step (2) can be performed in an ambient atmosphere. The treatment step (2) is particularly preferably performed in an atmosphere in which nitrogen purge is performed to reduce oxygen in order to suppress polymerization due to oxidation reaction.
Although there is no restriction | limiting in particular in the processing method in a process process (2), Standing or stirring processing can be mentioned. For example, a general batch reactor, a semi-batch reactor, or the like can be used. Moreover, the system which processes, extruding the slurry which consists of a plant-derived biomass-derived solid substance and an organic solvent or water and an organic solvent with a screw or a pump etc. is also applicable.

The reaction product obtained after the heat treatment in the treatment step (2) can be subjected to solid-liquid separation to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid.
In addition, the solid-liquid separation after the processing step (2) may include a step of washing the solid content obtained by the solid-liquid separation with water. This water washing process can be performed by adding 100 mass parts or more and 10000 mass parts or less of water with respect to 100 mass parts of solid content obtained after solid-liquid separation, and stirring. After stirring, the solid content and the liquid phase are separated by filtration.
As described above, the amount of water used in the washing step is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 1000 parts by mass or more and 5000 parts by mass or less, and further preferably 1000 parts by mass or more and 2000 parts by mass or less. If the amount of water used for water washing is 100 parts by mass or more, a sufficient cleaning effect can be obtained, and if it is 10000 parts by mass or less, it can be carried out without any problems in terms of equipment. By this water washing step, it is possible to further remove the organic solvent and to remove water-soluble components attached to the cellulose-containing solid.

A cellulose-containing solid can be obtained after solid-liquid separation after the heat treatment in the treatment step (2), or further through the water washing step. According to the manufacturing method according to the present embodiment, the cellulose-containing solid contained in the plant biomass can be recovered as a solid obtained as a residue in the aqueous phase.
Although there is no restriction | limiting in particular in the separation system in the manufacturing method which concerns on this embodiment, Filtration, a filter press, centrifugation, a dehydrator etc. can be mentioned.

The liquid phase obtained after the heat treatment in the treatment step (2) or after further water washing treatment contains lignin. For example, when a mixed solvent of water and an organic solvent is used and two phases are formed after the treatment, the organic phase obtained after separating the aqueous phase can be vaporized to remove the solvent to obtain solid lignin. it can. In addition, even when an organic solvent is used alone or when a mixed solvent with water is used, if the organic solvent is one phase after the heat treatment in the treatment step (2), the solvent is removed by vaporizing the organic solvent or the like. Then, solid lignin can be obtained by filtering the solid residue remaining in the water or by solid matter precipitated in water.

As described above, according to the production method of the present invention, hemicellulose, cellulose-containing solid and lignin can be produced as a plant-derived biomass-derived product. Each product is described in detail below.

<Characteristics of lignin>
The lignin obtained by the production method of the present invention has the following characteristics.
(11): The purity of lignin is 90% or more,
(12): Number average molecular weight is 650 or more, and (13): 5% thermogravimetric decrease starting temperature is 210 ° C. or more.
In the above, the purity of lignin is preferably 92% or more, and more preferably 94% or more. The number average molecular weight is preferably 700 or more, and more preferably 750 or more. Furthermore, the 5% thermogravimetric decrease starting temperature is preferably 215 ° C. or higher, more preferably 220 ° C. or higher.
In addition, each measuring method of the purity of the said lignin, a number average molecular weight, and a 5% thermogravimetric decrease start temperature is mentioned later.

<Characteristics of hemicellulose-derived saccharide and the obtained cellulose-containing solid>
According to the manufacturing method of this invention, the collection | recovery rate of hemicellulose origin saccharide | sugar with respect to the hemicellulose in plant biomass becomes 50 mass% or more. When the recovery rate of saccharides derived from hemicellulose is less than 50% by mass, saccharides that can contribute to fermentation decrease.
The cellulose-containing solid obtained by the production method of the present invention contains 60% by mass or more and 90% by mass or less of a cellulose degradation product obtained by decomposing cellulose and cellulose on the basis of the total amount of the cellulose-containing solid as a solid content. As other substances, lignin is contained in an amount of 5% by mass to 30% by mass, and hemicellulose and a hemicellulose decomposition product obtained by decomposing hemicellulose are contained in an amount of 0% by mass to 5% by mass. Moreover, the cellulose recovery rate in the cellulose containing solid with respect to the cellulose in plant-type biomass will be 70 mass% or more.
When the cellulose and the cellulose degradation product obtained by decomposing cellulose are less than 60% by mass, or when the lignin exceeds 30% by mass, the saccharification rate when glucose is obtained by enzymatic saccharification treatment decreases. If hemicellulose and the hemicellulose degradation product obtained by decomposing hemicellulose exceed 5% by mass, separation and removal of lignin bound to hemicellulose will be insufficient, and the saccharification rate when obtaining glucose by enzymatic saccharification will decrease. . Moreover, when a cellulose recovery rate is less than 70 mass%, the glucose recovery rate with respect to the cellulose in plant-type biomass falls.

<Uses of cellulose-containing solids>
Since the cellulose contained in the cellulose-containing solid obtained by the production method of the present invention has a low lignin content, it is suitably used for saccharification treatment with acids and enzymes. Moreover, the cellulose containing solid obtained by the manufacturing method of this invention is in the state which is easy to be defibrated compared with the cellulose containing solid obtained by other methods. For this reason, it has the advantage that application development is easy.
Further, ethanol, butanol, acetone, and the like can be obtained from the cellulose-containing solid obtained by the production method of the present invention using a known method.
Further, from the cellulose-containing solid obtained by the production method of the present invention, resin and fiber reinforcing materials such as cellulose nanofibers, rubber and tire reinforcing materials as a substitute for chemical fibers, food additives such as carboxymethylcellulose and oligosaccharides, lactic acid Chemical products such as succinic acid can be obtained.

<Uses of hemicellulose and lignin>
From the hemicellulose obtained by the production method of the present invention, food additives such as oligosaccharides and xylitol, and chemicals such as furfural can be obtained, which is useful.
The lignin obtained by the production method of the present invention can be specifically used as a water repellent material for fuel and cement. Further, it can be applied to phenol resin, epoxy resin, polyurethane resin base resin raw material, epoxy resin additive (curing agent), polyurethane resin modifier (flame retardant), thermoplastic resin additive, and the like. This is due to the characteristic that lignin has a phenolic structural unit.
A conventionally well-known method can be used about the use as a base resin raw material of lignin. As an example, a resin composition in which a known crosslinking agent typified by lignin and hexamethylenetetramine is blended can be mentioned.
You may mix | blend various fillers and the general phenol resin obtained industrially with the resin composition formed by mix | blending a lignin and a crosslinking agent as needed. Such a resin composition is used for heat insulating materials for homes, electronic parts, resin for flack sand, resin for coated sand, resin for impregnation, resin for laminating, resin for FRP molding, automobile parts, reinforcing material for automobile tires, etc. Can be used.
Moreover, application to an epoxy resin is also possible by introducing an epoxy group into lignin and using lignin as an epoxy resin curing agent. In addition, by introducing a vinyl group, a maleimide group, an isocyanate group or the like into lignin using a known method, it can be applied to a wider range of industrial resins.

Regarding the use as an additive, for example, conventionally known methods such as those described in JP-A-2014-15579 and International Publication No. 2016/104634 can be used. You may mix | blend various additives and a filler as needed with the resin composition formed by mix | blending a lignin and a thermoplastic resin.

[Resin composition]
In another embodiment of the present invention, a resin composition containing lignin obtained by the above production method is provided. Moreover, resin components, such as a thermoplastic resin and a thermosetting resin, may be contained other than the lignin obtained by the said manufacturing method. Components other than lignin will be described below.

<Thermoplastic resin>
The thermoplastic resin that can be blended in the resin composition according to the present embodiment is an amorphous thermoplastic resin having a glass transition temperature of 200 ° C. or lower, or a crystalline thermoplastic resin having a melting point of 200 ° C. or lower. Is preferred. Examples of the thermoplastic resin include polycarbonate resin, styrene resin, polystyrene elastomer, polyethylene resin, polypropylene resin, polyacrylic resin (polymethyl methacrylate resin, etc.), polyvinyl chloride resin, cellulose acetate resin, polyamide resin, Low melting point polyester resins (PET, PBT, etc.) represented by polyesters of combinations of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, polylactic acid and / or copolymers containing polylactic acid, acrylonitrile-butadiene -Styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS), fluororesin, silicon resin, polyimide resin, polybenzimi Tetrazole resins, polyamide elastomers, and copolymers thereof with other monomers.
The content of the thermoplastic resin in the resin composition according to the present invention is 30% by mass or more and 99.9% by mass or less with respect to the total amount of the resin composition from the viewpoint of obtaining remarkable fluidity and strength. It is preferably 40% by mass to 99.9% by mass, more preferably 45% by mass to 99.9% by mass, and particularly preferably 50% by mass to 99.9% by mass.
The resin composition according to the present embodiment may contain a resin, an additive and / or a filler compatible with the thermoplastic resin composition in addition to the above-described cellulose-containing solid and thermoplastic resin. Good.

<Thermosetting resin>
You may mix | blend the lignin reactive compound which has a functional group which can react with lignin as a thermosetting resin which can be mix | blended with the resin composition which concerns on this embodiment. Examples of the compound having a functional group capable of reacting with lignin include a compound that causes an electrophilic substitution reaction with a phenol compound, a compound having an epoxy group, a compound having an isocyanate group, and the like.
Since lignin has a phenolic structural unit, it can be applied as a base resin raw material such as phenol resin and epoxy resin, an additive (curing agent) of epoxy resin, and the like.
(Compound that causes electrophilic substitution reaction with phenolic compounds)
Examples of the compound that causes an electrophilic substitution reaction with a phenol compound include formaldehyde, a formaldehyde donating curing agent compound, or a formaldehyde equivalent compound. Commercially, hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde can be used.
Moreover, the resin composition according to the present embodiment may further contain a phenol resin in addition to lignin and hexamethylenetetramine. As described above, since lignin has a phenolic structural unit, the phenol resin is a lignin diluent, extender, etc., as long as the physical properties such as processability, strength, and heat resistance of the resin composition do not deteriorate. Can be used as

(Compound having an epoxy group)
The compound having an epoxy group belongs to a category called a so-called epoxy resin. Examples include 2,2-bis (4′-hydroxyphenyl) propane (referred to as bisphenol A), bis (2-hydroxyphenyl) methane (referred to as bisphenol F), 4,4′-dihydroxydiphenyl Sulfone (referred to as bisphenol S), 4,4′-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted and alkyl-substituted thereof, butanediol, ethylene glycol, A compound containing two or more hydroxyl groups in the molecule such as erythritol, novolak, glycerin, polyoxyalkylene and the like, and a glycidyl ether epoxy resin synthesized from epichlorohydrin, etc .; a compound containing two or more such hydroxyl groups in the molecule And lid Glycidyl ester epoxy resin synthesized from acid glycidyl ester, etc .; Glycidyl synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminomethylcyclohexane and epichlorohydrin Examples include epoxy resins containing glycidyl groups such as amine-based epoxy resins; epoxy resins containing no glycidyl groups such as epoxidized soybean oil, epoxidized polyolefin, vinylcyclohexenedioxide, and dicyclopentadiene dioxide. Among these, cresol novolac type and phenol novolac type epoxy resins having a similar chemical structure to lignin and good compatibility are preferable.

Moreover, the thermosetting resin composition may further contain a phenol resin in addition to the compound containing lignin and an epoxy group.
When the lignin contained in the thermosetting resin composition is a compound containing an epoxy group, a curing accelerator can be appropriately added according to the purpose of promoting the curing reaction. Specific examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,4). 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, tri Examples thereof include quaternary phosphonium salts such as phenylbenzylphosphonium salt, triphenylethylphosphonium salt and tetrabutylphosphonium salt, and metal compounds such as tin octylate. Examples of the counter ion of the quaternary phosphonium salt include halogen, organic acid ion, hydroxide ion and the like, and organic acid ion and hydroxide ion are particularly preferable.

(Compound having an isocyanate group)
The compound having an isocyanate group is obtained by reacting polyisocyanate or polyisocyanate with a polyol. Polyisocyanates include aromatic polyisocyanates such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI (MDI-CR), carbodiimide-modified MDI (liquid MDI), and norbornane diisocyanate (NBDI). Aliphatic polyisocyanates such as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), xylylene diisocyanate (XDI), and blocked isocyanates. be able to. Among these, tolylene diisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI) are preferably used.
The thermosetting resin composition may further contain a phenol resin in addition to lignin and an isocyanate compound.

A curing accelerator can be appropriately added to the thermosetting resin composition according to the purpose of accelerating the curing reaction. Examples of the curing accelerator include zirconium and aluminum organometallic catalysts, dibutyltin laurate, DBU phenol salts, octylates, amines, imidazoles, and the like. For example, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, zirconium tributoxyacetylacetonate, zirconium tetraacetylacetonate and the like are particularly preferable.

(Other resin components)
In addition to lignin, the resin composition according to this embodiment may contain a resin such as a phenol resin, a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, or a polyurethane resin.
Like lignin, it has a phenolic hydroxyl group, can react with lignin, and can also be used as a diluent for lignin. Therefore, phenol resins are preferred among the above resins.

<Inorganic filler, organic filler>
The resin composition according to the present embodiment may include a filler. The filler may be an inorganic filler or an organic filler.
As the inorganic filler, for example, silica powder such as spherical or crushed fused silica, crystalline silica, alumina powder, glass powder, glass fiber, glass flake, mica, talc, calcium carbonate, alumina, hydrated alumina, nitriding Examples thereof include boron, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, and magnesium oxide.
Examples of the organic filler include carbon fiber, aramid fiber, paper powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell / nut powder, chitin powder, and starch.
The inorganic filler and the organic filler may be contained singly or in combination, and the content is determined according to the purpose.

<Other additives>
Various additives can be added to the resin composition according to the present embodiment as long as the properties of a molded product obtained from the resin composition are not impaired. Further, depending on the purpose, a compatibilizer, a surfactant and the like can be added.
Compatibilizers used with thermoplastic resins include resins in which polar groups are introduced by adding maleic anhydride, epoxy, or the like to thermoplastic resins, such as maleic anhydride-modified polyethylene resins, maleic anhydride-modified polypropylene resins, and various commercially available phases. A solubilizer may be used in combination.
Examples of the surfactant include linear fatty acids such as stearic acid, palmitic acid, and oleic acid, and branched / cyclic fatty acids with rosins, but are not particularly limited thereto.
In addition to the above-mentioned additives, additives that can be blended include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, a release agent, and an antioxidant. Agents, plasticizers, stress reducing agents, coupling agents, dyes, light scattering agents, small amounts of thermoplastic resins, etc.

[Molding]
The molded article which concerns on embodiment of this invention is obtained from the resin composition containing the lignin obtained by the manufacturing method mentioned above. As an example of a molded product, a cured resin composition in which lignin and a crosslinking agent are blended, and various fillers and industrially obtained general phenol resins are blended as necessary, Examples thereof include those cured after being molded into a predetermined shape, and those molded after being cured.
The method for molding into a predetermined shape is not particularly limited as long as the resin composition can be molded. For example, when the resin composition is a thermosetting resin composition, examples of the method for molding into a predetermined shape include a compression molding method, an injection molding method, a transfer molding method, an intermediate molding method, and an FRP molding method. In addition, when the resin composition is a thermoplastic resin composition, examples of the method for molding into a predetermined shape include an extrusion molding method and an injection molding method.

As an example of a molded product, what is obtained by curing a resin composition in which lignin and a crosslinking agent are blended, various fillers and general phenol resins obtained industrially, if necessary, Examples thereof include those cured after being molded into a predetermined shape, those molded after being cured, and those obtained by molding a resin composition obtained by mixing lignin with a thermoplastic resin. Molded articles of such resin compositions include: heat insulating materials for housing, electronic parts, resin for flack sand, resin for coated sand, resin for impregnation, resin for lamination, resin for FRP molding, automobile parts, reinforcement of automobile tires It can be used for materials, OA equipment, machines, information communication equipment, industrial materials and the like.

[Method for producing glucose]
Glucose can be produced using the cellulose-containing solid obtained by the method for producing a cellulose-containing solid according to the embodiment of the present invention.

In the method for producing glucose according to the present embodiment, the conditions for the enzymatic saccharification treatment are as follows.
Cellulose contained in the cellulose-containing solid and the enzyme that acts on the cellulose degradation product obtained by decomposing cellulose may be 0.1% by mass or more and 200% by mass or less based on the total amount of the cellulose-containing solid. it can. Moreover, the enzyme activity used for an enzyme saccharification process can be 100 CUN / g or more and 10000 CUN / g or less. Furthermore, if the processing temperature in enzyme saccharification processing is 30 degreeC or more and 70 degrees C or less, an enzyme will activate and it can improve a saccharification rate. When the treatment time in the enzyme saccharification treatment is 12 hours or more and 168 hours or less, the enzyme is activated and the saccharification rate can be improved.

Hereinafter, the present embodiment will be described more specifically by way of examples, but the present embodiment is not limited to these.

[Production Example of Cellulose-Containing Solid]
<Production Example 1>
Processing step (1)
Plant-based biomass (for example, plant-based biomass such as bagasse) as a raw material is pulverized to a few mm or less as a pretreatment. After pulverization, water is added to obtain a raw material slurry having a solid concentration of about 15% by mass. To this raw slurry, phosphoric acid is added and mixed so that the pH in the raw slurry becomes 2.0.
The raw slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state. When the hemicellulose in the raw slurry is hydrolyzed, hydrothermal treatment is preferably performed at a temperature of 170 ° C.
Processing step (2)
Solid content obtained from the treatment step (1), a mixed solvent of water and 1-butanol prepared at a 1-butanol concentration of 34% by mass, sodium hydroxide so that the pH is 3, SUS (stainless steel with an internal volume of 0.92 L) ) Placed in batch-type apparatus. The total amount of solvent was 315 g. The raw material charge concentration was made as raw material / solvent = 1/10 (solid content charge concentration: 9.1% by mass).
After purging the inside of the SUS batch type apparatus with nitrogen, the temperature was raised to 200 ° C. and the treatment was performed for 2 hours. The treatment time was the elapsed time after reaching 200 ° C. The temperature was measured with a thermocouple.
After completion of the treatment, the SUS batch-type apparatus was cooled, and after the temperature dropped to near room temperature, the entire contents were taken out. After the treatment, the solid content and the liquid phase were separated by filtration.
200 g of water was added to the solid content, and after stirring for 30 minutes, the solid content and the liquid phase were separated by filtration. The said operation was repeated 3 times and the cellulose containing solid substance was obtained. The liquid phase was liquid / liquid separated into a water phase and a 1-butanol phase by a separatory funnel. The solvent of the 1-butanol phase was removed with an evaporator (70 ° C., water bath) and then vacuum-dried at 125 ° C. to obtain lignin.

<Production Example 2>
All in the same manner as in Production Example 1 except that the pH was adjusted to 4 in the treatment step (2).
<Production Example 3>
The same procedure as in Production Example 2 was conducted except that the 1-butanol concentration in the mixed solvent in the treatment step (2) was 50% by mass.

<Production Example 4>
It carried out similarly to manufacture example 3 except having used ethanol as an organic solvent which comprises the mixed solvent of a process process (2). Since the liquid phase after solid-liquid separation was a single phase, the organic solvent was removed with an evaporator, and the solid content precipitated in water due to the decrease in solubility was separated by solid-liquid separation by filtration. And vacuum drying to obtain lignin.

<Production Example 5>
Lignin was obtained by the same operation as in Production Example 4 except that acetone was used as the organic solvent constituting the mixed solvent in the treatment step (2).
<Production Example 6>
All operations were performed in the same manner as in Production Example 3, except that 2-methyl 1-propanol was used as the organic solvent constituting the mixed solvent in the treatment step (2).
<Production Example 7>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 5 in the treatment step (2).
<Production Example 8>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 6 in the treatment step (2).

<Production Example 9>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 7 in the treatment step (2).
<Production Example 10>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 10 in the treatment step (2).
<Production Example 11>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 12 in the treatment step (2).
<Production Example 12> (Only water is used in the treatment step (1), not an acidic aqueous solution)
First, plant-based biomass (for example, plant-based biomass such as bagasse) as a raw material is pulverized to several mm or less as a pretreatment. After pulverization, water is added to obtain a raw material slurry having a solid concentration of about 10% by mass.
The raw slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state. When the hemicellulose in the raw slurry is hydrolyzed, hydrothermal treatment is preferably performed at a temperature of 170 ° C. Thereafter, everything was carried out in the same manner as in Production Example 1 except that sodium hydroxide was not added to adjust the pH in (treatment step (2)).

<Production Example 13>
All in the same manner as in Production Example 1 except that sodium hydroxide was not added to adjust the pH in the treatment step (2).
<Comparative production example>
The same procedure as in Production Example 13 was performed except that the plant-based biomass as a raw material was treated with a mixed solvent of water and 1-butanol without going through the treatment step (1) which is a hydrothermal treatment step.

<Analysis of cellulose content in plant biomass and cellulose-containing solids>
The amount of cellulose in the plant biomass and cellulose-containing solid was calculated according to the constituent sugar analysis after the pretreatment shown below.
[Preprocessing]
As a pretreatment, a raw material to be a sample was pulverized using a Willet mill and dried at 105 ° C.
[Component sugar analysis]
An appropriate amount of a plant-based biomass or cellulose-containing solid sample was weighed, 72% sulfuric acid was added, and the mixture was allowed to stand at 30 ° C. with stirring as needed for 1 hour. The reaction solution was completely transferred to a pressure-resistant bottle while being mixed with pure water, treated in an autoclave at 120 ° C. for 1 hour, and then the filtrate and the residue were separated by filtration. Monosaccharides in the filtrate were quantified by high performance liquid chromatography. In addition, C6 polysaccharide (mainly glucan) was defined as cellulose, and C5 polysaccharide (mainly xylan) was defined as hemicellulose.
[Lignin]
The residue obtained by filtration in the process of constituent sugar analysis was dried at 105 ° C., the weight was measured, and the decomposition residue rate was calculated. Furthermore, the lignin content was calculated by correcting the ash content.

<Cellulose recovery rate>
Cellulose recovery rate (% by weight) = (cellulose-containing solids recovered amount (g) × cellulose ratio in cellulose-containing solids (% by weight) / 100) / cellulose amount in plant biomass (g) × 100
<Hydroxymethylfurfural production rate>
The concentration of hydroxymethylfurfural was calculated using a high performance liquid chromatograph (HPLC 1200 series, manufactured by Agilent).
Hydroxymethylfurfural production rate (mass%) = hydroxymethylfurfural concentration (mg / L) × 10−6 × solution volume (mL) / plant biomass (g) × 100

In Production Examples 1 to 12, it was found that the production of hydroxymethylfurfural due to excessive decomposition was suppressed and a high cellulose recovery rate was obtained.

Examples 1 to 13
[Evaluation method of the obtained cellulose-containing solid]
<Enzymatic saccharification treatment>
1 g (dry weight) of cellulose-containing solid was put into a 50 mL centrifuge tube and sterilized at 121 ° C. for 20 minutes. A similar sterilized acetate buffer solution was added to the centrifuge tube so that the solution volume was about 20 mL and pH 5, and then the enzyme amounts shown in Table 3 (manufactured by Nagase ChemteX Corporation, Cellizer ACE) Was introduced. The centrifuge tube was shaken in a thermostatic bath at 50 ° C. at 120 rpm for 72 hours.
When 1 ml of the enzyme is added to 4 ml of 0.625% sodium carboxymethylcellulose solution (pH 4.5) and allowed to act at 40 ° C. for 30 minutes, reduction corresponding to 1 μmol of glucose per minute The activity that generates force is denoted as 1 CUN. The enzyme has an enzyme activity of 1600 CUN / g or more.

<Analysis of the amount of glucose in the resulting xylose + xylooligosaccharide and cellulose-containing solid>
1. Sugar analysis Sugar (xylose, xylooligosaccharide, glucose) was analyzed by HPLC using the following conditions.
Measurement condition column: Showa Denko Shodex SP-G (guard column) + SP0810
Mobile phase: distilled water (HPLC grade)
Detector: RI (60 ° C in the cell)
Column temperature: 80 ° C
Injection volume: 50 μL
2. Sample Preparation Using a pipetter, collect 0.2 mL of sample (solution) in a 10 mL vial.
Add 1.8 mL of distilled water and mix well (10-fold dilution).
Collect in a vial.
3. Calculation method The glucose concentration (g-glucose / L) is calculated using a calibration curve.
Glucose recovery rate (%) = (glucose amount in cellulose-containing solid enzyme saccharified solution (g) × cellulose-containing solid material recovery rate (mass%) / 100) / glucose amount in plant biomass (g) × 100

In Examples 1 to 12 using the cellulose-containing solid produced by the production example of the present invention, the glucose recovery rate based on the amount of glucose in plant biomass obtained by enzymatic saccharification from the cellulose-containing solid shows a high value. It was. In Example 13 using the cellulose-containing solid obtained in Production Example 13 in which the pH was not adjusted in the treatment step (2), the total amount of cellulose-containing solid that can be recovered is lower than in other production examples. Therefore, when the amount of the enzyme is 0.1 mL, the absolute amount of cellulose that is decomposed to sugar is low, so that the glucose recovery rate is lower than others.

Example 9 and Comparative Example 1
(Xylose, xylooligosaccharide, glucose) recovery rate (%) = (xylose amount (g) in hydrothermal treatment liquid + xylooligosaccharide amount (g) in hydrothermal treatment liquid + (glucose amount in cellulose-containing solid enzyme saccharification solution) (G) × cellulose-containing solids recovery rate (mass%) / 100)) / (xylose amount in plant biomass (g) + glucose amount in plant biomass (g)) × 100

According to the production method of the present invention, saccharide can be efficiently recovered on the basis of plant biomass because the hemicellulose-derived saccharides (xylose and xylooligosaccharide) can be suppressed and recovered.

<Measurement of lignin purity>
It carried out similarly to the above <Composition analysis of a raw material>.
<Number average molecular weight>
The number average molecular weight of the above lignin was measured by a gel permeation chromatograph (GPC) using a tetrahydrofuran solvent (measurement temperature 40 ° C., detector RI). The number average molecular weight is a polystyrene-equivalent number average molecular weight.
<Thermal weight decrease start temperature (Td5)>
The 5% thermogravimetric decrease starting temperature (Td5) was measured with EXSTAR6000 TG / DTA6200 manufactured by SII. About 10 mg of a sample was weighed in a Pt pan, measured at a temperature increase rate of 10 ° C./min, measurement atmosphere: air 200 mL / min, temperature 35 ° C. to 800 ° C., and a temperature at which the weight decreased by 5% was determined.
<Phenolic hydroxyl group equivalent>
A solvent mixed with deuterated chloroform, pyridine and cyclohexanol (internal standard) is added to the purified lignin, and 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxa is used as a derivatization reagent. Phosphorane was added and heated at 50 ° C. for 1 hour. Thereafter, 31PNMR measurement was performed under the following measurement conditions.
Pulse width: 30 °
Repetition time: 2 seconds Measurement range: -60 to 200 ppm
Integration number: 200 times The signal derived from the internal standard cyclohexanol was 145.2 ppm, 144.7 to 136.6 ppm was assigned as phenolic hydroxyl group (Ph-OH), and the phenolic hydroxyl group equivalent (g / eq) was calculated from the integrated value. ) Was calculated.

As can be seen from Table 4, lignin having high heat resistance was obtained. Moreover, since secondary modification | denaturation is not performed in this manufacturing method, it has a high amount of phenolic hydroxyl groups. Therefore, it can be suitably used as a material.

Example 9 and Comparative Example 1
[Evaluation of thermosetting resin composition containing hexamethylenetetramine]
A thermosetting resin composition was prepared using the lignin obtained in Production Example 9 and Comparative Production Example. Moreover, the hardened | cured material was produced and the physical property was evaluated.
<Formulation of thermosetting resin composition and molding method of cured product>
Each component was put in a mortar at the blending ratio shown in Table 2, pulverized at room temperature, mixed, mixed at 100 ° C. for 5 minutes using an open roll kneader, and then cooled to room temperature. The mixture was pulverized in a mortar, sandwiched between aluminum plates coated with a release agent, and molded at 150 ° C. for 60 minutes under reduced pressure using a vacuum press. After molding, it was treated at 200 ° C. for 120 minutes to obtain a molded product.
<Bending strength measurement method>
A 5 mm × 50 mm × 1 mm sample was cut out from the obtained molded product, and the bending strength was measured using an Instron 5566 under conditions of a three-point bending mode, a span of 30 mm, and a speed of 2 mm / min.
<Measuring method of glass transition temperature>
The glass transition temperature was measured by the solid viscoelastic method. A sample of 5 mm × 30 mm × 1 mm was cut out from the obtained molded product, and the temperature was raised to 0 ° C. to 300 ° C. or 2 ° C./min until reaching the limit minimum elastic modulus using DMA8000 (manufactured by PerkinElmer Japan). Measurement was performed at 1 Hz. The obtained tan δ peak temperature was defined as the glass transition temperature (Tg).

As can be seen from the results in Table 5, in Example 13 using lignin obtained by the production method of the present invention, a molded product having high heat resistance and excellent physical properties was obtained.

According to the present invention, it is possible to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the excessive decomposition of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharide and the cellulose-containing solid.

Claims (17)

1. A treatment step (1) for separating hemicellulose from plant biomass;
   Processing step (2) in which the solid content obtained from the processing step (1) and an organic solvent alone or a solvent selected from a mixed solvent of an organic solvent and water are mixed and subjected to heat treatment.
   And a method for producing a plant-derived biomass-derived product.
2. The method for producing a plant biomass-derived product according to claim 1, wherein after the treatment step (2), solid-liquid separation is performed to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid.
3. The method for producing a plant biomass-derived product according to claim 2, wherein solid lignin is obtained by removing a solvent from the lignin-containing solution.
4. The method for producing a plant biomass-derived product according to any one of claims 1 to 3, wherein the plant biomass is a herbaceous biomass.
5. The method for producing a plant-based biomass-derived product according to any one of claims 1 to 4, wherein in the treatment step (1), hydrothermal treatment is performed as a treatment for separating hemicellulose.
6. The plant-derived biomass-derived production according to claim 5, wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam explosion, and hydrothermal treatment using an acidic aqueous solution. Manufacturing method.
7. The method for producing a plant biomass-derived product according to claim 6, wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from inorganic acids and organic acids.
8. The pH of the system from after the separation of hemicellulose in the treatment step (1) to before the mixing of the solid content and the solvent obtained from the treatment step (1) in the treatment step (2), or in the treatment step (2). The plant-derived biomass-derived product according to any one of claims 1 to 7, wherein the pH of the system when mixing the solid content obtained from the step (1) and the solvent is adjusted using a basic substance. Manufacturing method.
9. The method for producing a plant-based biomass-derived product according to claim 8, wherein in the treatment step (2), the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed is adjusted.
10. The method for producing a plant-derived biomass-derived product according to claim 8 or 9, wherein the pH of the system after adjusting the pH with the basic substance is 3 or more and 12 or less.
11. The organic solvent used in the treatment step (2) is at least one selected from ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and acetone. The manufacturing method of the plant-derived biomass origin product of description.
12. The method for producing a plant biomass-derived product according to any one of claims 1 to 11, wherein the treatment step (2) is performed under the following conditions A to C.
    Condition A: The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is 1% by mass or more and 50% by mass or less.
    Condition B: treatment temperature is 100 ° C. or more and 300 ° C. or less, and condition C: treatment time is 0.1 hour or more and 10 hours or less.
13. A method for producing glucose, wherein a cellulose-containing solid obtained by the production method according to any one of claims 2 to 12 is subjected to enzymatic saccharification treatment to obtain glucose.
14. A resin composition comprising the lignin obtained by the method according to any one of claims 2 to 12.
15. Lignin satisfying the following (11) to (13).
    (11): The purity of lignin is 90% or more,
    (12): Number average molecular weight is 650 or more, and (13): 5% thermogravimetric decrease starting temperature is 210 ° C. or more.
16. A resin composition comprising the lignin according to claim 15.
17. A molded product comprising the resin composition according to claim 14 or 16.